One objective of this research project is the delineation of the scope, mechanism, and synthetic utility of the highly exothermic (3,3) sigmatropic rearrangemens of N-aryl (and N-vinyl)-O-vinylhydroxylamines and related compounds to 1,4-imino ketones. The products resulting from the N-aryl substrates are either N-substituted indoles or aniline derivatives having a carbonyl-functionalized side-chain in the ortho position. The scope of this new indole synthesis and its application to the synthesis of mitomycin-like indoles and certain indole alkaloids is being investigated. Synthetic routes to the virtually unknown N,O-divinylhydroxylamines are under study in order to examine the rearrangement with non-aromatic substrates and to effect a direct 1,4-diketone synthesis. The interaction of N-arylhydroxylamines and hydroxamic acids with certain activated heterocycles is to be studied. The mechanisms and products of the reaction may have a bearing on the mode of action of the polycyclic aromatic hydroxylamine class of chemical carcinogens.